Bis-aryl methylene malononitriles



United States Patent BIS-ARYL METHYLENE MALONONITRILES Albert F. Strobe], Delmar, and Sigmund Catino, Castleton, N.Y., assignors to General Aniline & Film Corporation, New York, N.Y., a corporation of Delaware No Drawing. Continuation-impart of application Ser. No.

198,755, May 31, 1962. This application Jan. 23, 1967,

Ser. No. 610,765

16 Claims. (Cl. 260-248) ABSTRACT OF THE DISCLOSURE Substantially colorless compounds which exhibit a prominent absorption peak between 250' m and 400 m and which are outstanding absorbent-s for ultra-violet radiation and as stabilizers for organic materials against the degradative effect of such radiation are characterized as monocyclicheterocyclic, aryl methylene malononitriles, said heterocyclics being of the group containing 5 and 6 members in the ring and wherein the hetero atom is at least one of the group of oxygen, nitrogen and sulfur.

This invention relates to new and useful compounds which impart to organic materials superior resistance to degradation and deterioration when they are exposed to actinic radiation, and in particular to ultra-violet radiation. This invention further relates to processes for the preparation of new and useful compounds of the type hereinbefore described. The compounds with which this invention is concerned are characterized as aryl hetero methylene malononitriles.

While various organic compounds exhibit the power to absorb electromagnetic radiations Within the band of 2900 to 3700 A. and when incorporated in various plastic materials such as transparent sheets, the resultant sheet acts as a filter for all of the radiation passing through and will transmit only such radiations as are not absorbed by the sheet and/or the absorbing agent. It is thus possible to screen out undesirable radiations and utilize the resulting transparent sheet as a filter in many technical and commercial applications such as wrappings for food products and the like.

Numerous organic compounds have been suggested s absorbents for the range of radiations described above, which range is designated as the ultra-violet range. Such uses include incorporation in plastic sheet materials and the stabilization in general of transparent plastic bodies.

By far, the greatest concern with respect to ultra-violet radiations is with those radiations which come from the sun. Most of these radiations have wave lengths between 250 and 400 millimicrons. The effects of such radiation on the human skin, producing sunburn and suntan are of course well known. Other effects, however, of great commercial importance relate to the photochemical degradation caused by ultra-violet radiation. Many commercial products are either unstable when subjected to such radiations, or are affected to the extent that they become undesirable or unsalable. Many plastic materials, when exposed to this radiation, undergo substantial degradation resulting in the development of undesirable color bodies and subsequent loss of transparency. Food products, in addition to becoming discolored, often become unfit for human consumption. Thus, prolonged exposure of fruits, edible oils, butter and other prepared foods will spoil and turn rancid on exposure to ultraviolet light. It is well known that colored objects such as dyed textiles will fade on exposure to sunlight, and in particular to ultra-violet light. Many plastics, in addition to developing color formation and reduction in transparency, become brittle, lose their elasticity, crack and eventually completely deteriorate on exposure to sunlight. Paints, varnishes, lacquers and the like also are prone to these effects, even though here the transparency property may not be paramount.

We have discovered that by combining aryl hetero methylene mal-ononitriles with organic materials, there results compatible combinations with a vast number of film forming plastics, resins, gums, waxes and the like, which combinations further exhibit outstanding ultraviolet absorbing properties within the generally encountered ultraviolet regions of 250 to 400 millimicrons. The compounds with which this invention is concerned, even though they exhibit outstanding absorbing properties close to the visible region of the electro magnetic field, nevertheless are essentially colorless compounds and can be em-. ployed with the assurance that they will not contribute to color in normally colorless formulations, nor will they affect the color of a colored formulation such as a paint film or a dyed textile. Many of the compounds of this invention also absorbs some visible light on the violet end of the spectrum which renders them particularly useful in many formulations which are susceptible to visible light degradation. Thus polyesters and polyethylene are known to be so characterized, and the stabilization of these materials is extremely successful when using the compounds herein contemplated.

The compounds of this invention, additionally, are outstanding in that they do not require a phenolic hydroxyl group in order to achieve light stability. The heretofore used hydroxybenzophenone absorbers must have such a grouping. The presence of an hydroxyl which is capable of salt formation renders these absorbers unsuitable for use in alkaline media and particularly in alkaline plastic materials such as epoxys, melamines and the like. While the compounds of the present invention do not require an hydroxyl group, the presence thereof is not disadvantageous, or a detriment where alkaline sensitivity is no problem.

It is therefore an object of the present invention to provide new and useful compounds characterized by outstanding ultra-violet absorbing properties.

It is still another object of this invention to provide new and useful aryl hetero methylene malononitriles which are outstanding ultra-violet absorbing compounds.

It is a still further object of the present invention to provide processes for the preparation of new and useful ultraviolet absorbing compounds.

It is a still further object of the present invention to provide processes for the preparation of new and useful ultraviolet absorbing compounds which are characterized as aryl hetero methylene malononitriles.

Other objects will appear hereinafter as the description proceeds.

The aryl hetero methylene malononitriles which are contemplated in this invention exhibit a prominent peak or peaks between 250 A. and 400 A. and are devoid of nitro groups and nuclear bonded amino groups and have the following general formula:

(HET) CN wherein (HET) represents a 5- or 6-membered heterocyclic nucleus or a benzo (5- or 6-membered) heterocyclic nu cleus containing at least one pair of conjugated double bonds and wherein the hetero atoms are oxygen, nitrogen and/or sulfur and Ar represents an aromatic car-bocyclic nucleus.

Examples of suitable heterocycles are: thiophene, furane, pyrrole, rx-pyran, a-pyr-one, pyridine, LQ-dihydropyridine, oxazole, th i'azole, isoxazole, isothiazole, pyrazole, 3-isopyrazole, imidazole, 2-isoimidazo'le, 1,2,3-tri- 7 4-tertiarybutyl-3-chloro-2-hydroxyphenyl-2-luryl ketone -ethyl-2-thienyl-p-methoxyphenyl ketone 6-allyloxy-2,4-xylyl-2-furyl ketone 3-chloro-4-methoxy-4-biphenyl-yl-2-thienyl ketone o-chlorophenyl-5-chloro-2-thienyl ketone In addition to the above contemplated derivatives, polyoxyalkylated derivatives thereof are within the purview of this invention. Any of the aforementioned compounds containing at least one reactive hydrogen atom may be reacted with an alkylene oxide or a compound functioning as an oxide (or mixtures thereof) such as: ethylene oxide, phopylene oxide, butylene oxide, butylene dioxide, isobutylene oxide, giycidol, epichlorohydrin butadiene dioxide, isobutylene oxide, styrene oxide, and the like to yield the corresponding polyoxyalkylated products.

Among the types of compounds which are reactive in this manner are: hydroxy compounds, amide compounds, carboxycompounds, etc. From one to about 200 moles of oxyalkylating agent may be condensed with the said reactive compounds.

The following examples will serve to illustrate the present invention without being deemed limitative thereof. Parts are by weight unless otherwise indicated.

Example 1 I. Preparation of pheny1-2-thieny1methylene malonouitrile Into a dry flask fitted with a stirrer, thermometer, reflux condenser to the top of which is attached a drying tube containing anhydrous calcium chloride, and heating mantle, there are added 20.0 grams of a-cyano-B-phenylfl-(2-thienyl) acrylamide and 67 grams mls.) of phosphorus oxychloride. The reaction mixture is heated to 60 C. and stirred until complete solution occurs. Then the stirring is continued for hr. longer at 60 C. The reaction mixture is cooled to room temperature and drowned into 500 grams of ice-water slush. The slurry is stirred 1 hrs. at 05 C., filtered and washed with 1000 grams of water. The crude product is dried at 80 C. and then stirred with 300 rnls. benzene. The slurry is clarified to remove insolubles. The clear benzene extract is evaporated and the residue is recrystallized from 375 mls. isopropanol using animal charcoal. The product is filtered from isopropanol at 5 C. and dried at 80 C. There is obtained 11.9 grams of phenyl-2-thienylmethylene malononitrile. The product has a melting point at 139.2140.8 C. and a K max. in methanol=79.4 at 354 II. Preparation of In a 500 ml. three-necked flask fitted with a stirrer, thermometer, Barrett type water separator (which allows the upper layer to be returned to the reaction flask), reflux condenser and heating mantle are added 47.28 grams of phenyl-Z-thienyl ketone (M.W.=189, =0.25 mole), 21.0 grams of cyanoacetamide (M.W.=84, =0.25 mole), 4.0 grams of ammonium acetate, 24 mls. of glacial acetic acid and mls. benzene. The reaction mixture is then heated to vigorous reflux and stirred for hours at 98-100 C. During this period 1.0 gram additions of ammonium acetate are made after 7 hours, 25 hours and 30 hours. The benzene is then steam distilled from the reaction mixture. The residue after steam distillation is filtered at 35 C. The solid material is Washed on the funnel with 200 mls. of water and then ground in a mortar to break up lumps. This material is then heated to C. with 250 mls. isopropanol, cooled to 5 C. After drying in air at C. there is obtained 44.4 grams of occyano-B-phenyl- -(2-thienyl) acrylamide which melts at 195.3 C.197 C.

Example 2 Example 1 is repeated except that the ketone employed in the preparation of the intermediate acrylamide is 5- bromo-2-thienyl ketone.

Example 3 Example 2 is repeated employing the following ketones:

Example 4 The product of Example 1 is used in a nitrocellulose lacquer as follows:

A mixture of 20 parts of solution I and 80 parts of solution II is prepared wherein solution I consists of:

46 parts /2 sec. nitrocellulose 4 parts product of Example 1 35 parts of Cellolyn 502 (non-drying plasticizing alkyd resin of Hercules Powder Co.)

15 parts dibutyl phthalate and solution II consists of 35 parts butyl acetate 15 parts butanol 50 parts toluene The resulting lacquer solution is drawn out on a metal plate with a Bird film application to give a 3 mil film. A similar film is prepared without the product of Example 1. Upon exposure to ultraviolet light, the latter film yellows and deteriorates before any visible signs of yellowing are observed in the protected film.

Example 5 Example 2 is repeated employing as the ketone, p-(2 ethylhexyloxy)-phenyl-2-thienyl ketone.

Example 6 The product of Example 5 is incorporated into polyethylene by melting at C. a mixture of 99.7 g. of polyethylene wax, PT-95504 (Semet-Solvay), and 0.3 g. of absorber. The material is then pressed out in a Carver press to give a film of about 0.03 in. thick. The polyethylene film is well stabilized to ultra-violet light and admirably protects food packaged therein.

Example 7 The product of Example 3(e) is incorporated into a synthetic latex as follows:

A 50% dispersion of the absorber of Example 3(e) is made by kneading 20 g. of the compound with 20 g. of formaldehyde-naphthalene-2-sodium sulfonate (Tamol NNO) in a We-rner-Pfleiderer mixer for several hours in the presence of sufficient water to keep the material in a viscous state. The material is then evaporated to dryness to give the dispersed form of the absorber. The dispersed absorber is then incorporated into an acrylonitrilebutadiene latex (Chemi-gum 247) employing of the absorber based on the weight of the latex. The latex is then sprayed onto leather. The film prepared in this manner shows less tendency to yellow on exposure to light than similar film prepared in the same manner but omitting the ultra-violet absorber.

Example 8 Barium cadmium stabilizer (Advance BS-105) 3.5 Celogen (p,p' oxybis(benzenesulfonyl)hydrazide) 35 The sponge is squeezed free of solvent and dried. It is much more stable to ultra-violet light than untreated material.

Example 9 The product otf Exa'mple 3(i) is oxyalkylated by adding 5 moles of ethylene to one mole of product containing 1.5% potassium hydroxide while maintaining the mixture in an autoclave .at 80 C. The final product contains 5 'oxyethyl groups.

Example 10 Example 9 is repeated using 10 moles oi ethylene oxide. The final product contains 10 oxyethyl groups.

Example 11 Example 9 is repeated using 30 moles of ethylene oxide. The final product contains 30 oxyethyl groups.

Example 12 Example 9 is repeated using 100 moles of ethylene oxide. The final product contains 1 00 oxyethyl groups.

Example 13 Example 9 is again repeated employing 200 moles of ethylene oxide. The final product contains 200 oxyethyl groups.

Example :14

The final product of Example 1O is further reacted with 5 moles of propylene oxide to yield a product having 5 terminal oxypropyl groups.

Example 15 The product of Example 10 is dispersed in water (2 g./ 100 g. water) and is used to treat paper, cotton, and gelled regenerated cellulose. Excellent protection against ultra-violet light degradation is obtained.

Example 16 The product of Example 11 is employed in formulating liquid detergent as follows:

The final formulation shows no degradation when exposed to ultraviolet light for hours.

Example 17 2 g. of the product of Example 2 is mixed with 100 g. of granular high molecular weight formaldehyde polymer (-Delrin). Excellent stabilization of the polymer is obtained.

The compounds of this invention are soluble in many dive'rse types of polymers, rcsins, waxes and the like, and therefore they are particularly suitable and adaptable for the stabilization of such materials as exemplified above. The non-oxyalkylated products are insoluble in water. Those compounds which contain lesser amounts of oxyalkyl groups, that is, up to about 4-6 groups per molecule, are in general less soluble in the non-polar solvents but are readily dispersi ble in water. The compounds containing larger amounts of alkylene oxide, that is, above about 6 moles thereof per mole of base compound, range from soluble in water with the solubility increasing as the number of oxyalkylene groups increases.

The ultra-violet absorbing compounds of the present invention may be used to stabilize all organic materials which are susceptible to ultra-violet degradation and are particularly useful in the stabilization of resins and plas tics, whether they be in the form of films or molded products and either clear, opaque, semi-opaque or translucent. Foam, plastics and fibers are also admirably stabilized by these compounds. Pigments, polishes, creams, lotions, paints, enamels, varnish films and dyestufls when susceptible to ultra-violet degradation have been found to be excellently stabilized by the compounds of the present invention. The amount of stabilizer to be incorporated in such compositions is not critical except that sufiicient should be present to eifect an acceptable degree of stabilization and no more should be used than is necessary to obtain such results. In general, between about 0.1% and 10% by weight based upon the organic solids weight to be stabilized may be used.

Other variations in and modifications of the described processes which will be obvious to those skilled in the art can be made in this invention without departing from the scope or spirit thereof.

We claim:

1. An essentially colorless compound exhibiting a prominent absorption peak between 250 my and 400 mp. of the formula:

(HET) oN Ara ON (a) wherein (HET) represents a he'terocyclic nucleus containing at least one pair of conjugated double bonds and selected from the group consisting of 5- 'and 6-membered monocyclic hetero cycle's containing as the hetero atom at least one member selected from the group consisting of oxygen, nitrogen and sulfur, and the corresponding benzomon'ocyclic heterocycles, and

(b) Ar is an aromatic, canbo'cyclic nucleus of up to 14 carbon atoms, said nuclei being devoid of n'itro and nuclear .bonded amino groups.

2. A compound as defined in claim 1 wherein (HET) is 'monocyclic.

3. A compound as defined in claim 1 wherein (HET) is bicyclic.

4. A compound as defined in claim 1 wherein (HET) is a sulfur heterocycle.

5. A compound as defined in claim 1 wherein (HET) is a nitrogen heterocycle.

6. A compound as defined in claim 1 wherein (HET) is an oxygen heterocycle.

7. A compound as defined in claim 1 wherein Ar is a phenyl nucleus.

1 1 1 2 8. A compound as defined in claim 1 wherein Ar is References Cited a naphthyl nucleus.

9. A compound as defined in claim 1 wherein (HET) UNITED STATES PATENTS is a thienyl nucleus and Ar is a phenyl nucleus. 2,973,462 4/ 1961 Barman 6t 31 260-3452 10. A compound as defined in claim 1 wherein (HET) 5 3,022,318 2/1962 fl 'm n 6t 1 2 345.2 is a furyl nucleus and Ar is a phenyl nucleus. 3,072,431 1/1963 Befmfln 96 11. A compound as defined in claim 9 wherein (HET) 3,085,469 4/1963 Carlson 8824 is Z-thienyl and Ar is phenyl.

12. A compound as defined in claim 9 wherein (HET) OTHER RE EREN E 15 Y 3 and z is p yp 10 Fieser et 211., Organic Chemistry (Heath, Boston, 1950),

13. A compoundas defined in claim 9 wherein (HET) pp 7 732' is zsdlmethyl'githlenyl and Arz Phenyl' Cotton et al., Adv. Inorg. Chem. ('Interscience, 1962),

14. A compound as defined in claim 9 wherein (HET) Pp 385 389 is 2,5-dimethyl-3 thienyl and Ar is p-ethylphenyl. l

15. A compound as defined in claim 9 wherein (HET) 15 T RM MI T A P is 2,5-dimethyl-3-thicnyl and Ar;,; is p-methoxyphenyl no A LES 6 Hmmy Exammel' 167 A compound as defined in claim 10 wherein (HET) SHURKO, Assistant Examllle is 2-uryl and Ar; is 3,4-dimethoxyphenyl. 

